Process for preparing compositions useful as intermediates for preparing lubricating oil and fuel additives

ABSTRACT

A process for reacting olefinic compounds, certain carboxylic reactants, and aldehydes or ketones and products prepared by the process. The compositions of the process are useful as intermediates for the preparation of additives for lubricants and fuels.

FIELD OF THE INVENTION

This invention relates to a process for preparing compositions which areuseful as intermediates for the preparation of low chlorine containingadditives for lubricating oils and normally liquid fuels, compoundsprepared by the process, and coupled lactone compounds.

BACKGROUND OF THE INVENTION

Numerous types of additives are used to improve lubricating oil and fuelcompositions. Such additives include, but are certainly not limited todispersants and detergents of the ashless and ash-containing variety,oxidation inhibitors, anti-wear additives, friction modifiers, and thelike. Such materials are well known in the art and are described in manypublications, for example, Smalheer, et al, "Lubricant Additives",Lezius-Hiles Co., Cleveland, Ohio, USA (1967); M. W. Ranney, Ed.,"Lubricant Additives", Noyes Data Corp., Park Ridge, N.J. USA (1973); M.J. Satriana, Ed., "Synthetic Oils and Lubricant Additives, Advancessince 1979, Noyes Data Corp., Park Ridge N.J. USA (1982), W. C. Gergel,"Lubricant Additive Chemistry", Publication 694-320-65R1 of The LubrizolCorp., Wickliffe, Ohio, USA (1994); and W. C. Gergel et al, "LubricationTheory and Practice" Publication 794-320-59R3 of The Lubrizol Corp.,Wickliffe, Ohio, USA (1994); and in numerous United States patents, forexample Chamberlin, III, U.S. Pat. No. 4,326,972, Schroeck et al, U.S.Pat. No.4,904,401, and Ripple et al, U.S. Pat. No. 4,981,602. Many suchadditives are frequently derived from carboxylic reactants, for example,acids, esters, anhydrides, lactones, and others. Specific examples ofcommonly used carboxylic compounds used as intermediates for preparinglubricating oil additives include alkyl-and alkenyl substituted succinicacids and anhydrides, polyolefin substituted carboxylic acids, aromaticacids, such as salicylic acids, and others. Illustrative carboxyliccompounds are described in Meinhardt, et al, U.S. Pat. No. 4,234,435;Norman et al, U.S. Pat. No. 3,172,892; LeSuer et al, U.S. Pat. No.3,454,607, and Rense, U.S. Pat. No. 3,215,707.

Many carboxylic intermediates used in the preparation of lubricating oiladditives contain chlorine. While the amount of chlorine present isoften only a very small amount of the total weight of the intermediate,the chlorine frequently is carried over into the carboxylic derivativewhich is desired as an additive. For a variety of reasons, includinggovernment regulation, environmental concerns, and commercial reasonsthe industry has been making efforts to reduce or to eliminate chlorinefrom additives designed for use as lubricant or fuel additives.

Accordingly, it is desirable to provide low chlorine or chlorine freeintermediates which can be used to prepare low chlorine or chlorine freederivatives for use in lubricants and fuels.

The present invention provides a method for preparing compounds whichmeet this requirement.

B. B. Snider and J. W. van Straten, J. Org. Chem., 44, 3567-3571 (1979)describes certain products prepared by the reaction of methyl glyoxylatewith several butenes and cyclohexenes. K. Mikami and M. Shimizu, Chem.Rev., 92, 1021-1050 (1992) describe carbonyl-ene reactions, includingglyoxylate-ene reactions. D. Savostianov (communicated by P.Pascal), C.R. Acad. Sc. Paris, 263, (605-7) (1966) relates to preparation of someα-hydroxylactones via the action of glyoxylic acid on olefins. M.Kerfanto et. al., C. R. Acad. Sc. Paris, 264, (232-5) (1967) relates tocondensation reactions of α-α-di-(N-morpholino)-acetic acid andglyoxylic acid with olefins.

SUMMARY OF THE INVENTION

The present invention relates to a process for preparing compoundsuseful as intermediates for preparing performance improving additivesfor lubricants and fuels which comprises reacting, optionally in thepresence of an acidic catalyst selected from the group consisting oforganic sulfonic acids, heteropolyacids, and mineral acids,

(A) at least one olefinic compound of the general formula

    (R.sup.1)(R.sup.2)C═C(R.sup.6)(CH(R.sup.7)(R.sup.8))

wherein each of R¹ and R² is, independently, hydrogen or a hydrocarbonbased group and each of R⁶, R⁷ and R⁸ is, independently, hydrogen or ahydrocarbon based group;

(B) at least one carboxylic reactant selected from the group consistingof compounds of the formula

    R.sup.3 C(O)(R.sup.4).sub.n C(O)OR.sup.5                   (IV)

and compounds of the formula ##STR1## wherein each of R³, R⁵ and each R⁹is independently H or a hydrocarbyl group, R⁴ is a divalenthydrocarbylene group, and n is 0 or 1 in amounts ranging from 0.6 moles(B) per mole of (A) to 1.5 moles (B) per equivalent of (A); and fromabout 0.5 to about 2 moles, per mole of (B), of

(C) at least one aldehyde or ketone; as well as products obtained by theprocess of the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

As used herein, the terms "hydrocarbon", "hydrocarbyl" or "hydrocarbonbased" mean that the group being described has predominantly hydrocarboncharacter within the context of this invention. These include groupsthat are purely hydrocarbon in nature, that is, they contain only carbonand hydrogen. They may also include groups containing non-hydrocarbonsubstituents or atoms which do not alter the predominantly hydrocarboncharacter of the group. Such substituents may include alkoxy-, nitro-,etc. These groups also may contain hetero atoms. Suitable hetero atomswill be apparent to those skilled in the art and include, for example,sulfur, nitrogen and oxygen. Therefore, while remaining predominantlyhydrocarbon in character within the context of this invention, thesegroups may contain atoms other than carbon present in a chain or ringotherwise composed of carbon atoms.

In general, no more than about three non-hydrocarbon substituents orheteroatoms, and preferably no more than one, will be present for every10 carbon atoms in the hydrocarbon, hydrocarbyl or hydrocarbon basedgroups. Most preferably, the groups are purely hydrocarbon in nature,that is they are essentially free of atoms other than carbon andhydrogen.

Throughout the specification and claims the expression soluble ordispersible is used. By soluble or dispersible is meant that an amountneeded to provide the desired level of activity or performance can beincorporated by being dissolved, dispersed or suspended in an oil oflubricating viscosity or in a normally liquid fuel. Usually, this meansthat at least about 0.001 % by weight of the material can beincorporated in a lubricating oil or normally liquid fuel. For a furtherdiscussion of the terms oil soluble and dispersible, particularly"stably dispersible", see U.S. Pat. No. 4,320,019 which is expresslyincorporated herein by reference for relevant teachings in this regard.

As noted hereinabove, provided by this invention is a process forpreparing low chlorine or chlorine free compositions useful asintermediates for preparing low chlorine or chlorine free additives forlubricating oil and fuel compositions.

The Process

In one embodiment, the present invention relates to a process comprisingreacting, optionally in the presence of an acidic catalyst selected fromthe group consisting of organic sulfonic acids, heteropolyacids, andmineral acids,

(A) at least one olefinic compound of the general formula

    (R.sup.1)(R.sup.2)C═C(R.sup.6)(CH(R.sup.7)(R.sup.8))

wherein each of R¹ and R² is, independently, hydrogen or a hydrocarbonbased group and each of R⁶, R⁷ and R⁸ is, independently, hydrogen or ahydrocarbon based group

(B) at least one carboxylic reactant selected from the group consistingof compounds of the formula

    R.sup.3 C(O)(R.sup.4).sub.n C(O)OR.sup.5                   (IV)

and compounds of the formula ##STR2## wherein each of R³, R⁵ and each R⁹is independently H or a hydrocarbyl group, R⁴ is a divalenthydrocarbylene group, and n is 0 or 1 in amounts ranging from 0.6 moles(B) per mole of (A) to 1.5 moles (B) per equivalent of (A); and fromabout 0.5 to about 2 moles, per mole of (B), of

(C) at least one aldehyde or ketone.

Reactants (A), (B), and (C) may be present at the outset of the reactionor (A) and (B) may be reacted first followed by reaction with (C). Underthese conditions, all of (A) and (B) may be present at the same time;however, it has been found that improvements in yield and purity of theproduct arising from the reaction of (A) and (B) may be attained whenthe carboxylic reactant (B) is added to the olefinic compound (A) eitherportionwise or continuously over an extended period of time, usually upto about 10 hours, more often from 1 hour up to about 6 hours,frequently from about 2 to about 4 hours.

The process may be conducted in the presence of an azeotroping solvent.Well known azeotroping solvents include toluene, xylene, cyclohexane,etc. Cyclohexane is preferred.

The Catalyst

The first step of the process of this invention is optionally conductedin the presence of an acidic catalyst. Acid catalysts, such as organicsulfonic acids, for example, paratoluene sulfonic acid, methane sulfonicacid and sulfonated polymers such as those marketed under the tradenameAMBERLYST® (Rohm & Haas), heteropolyacids, the complex acids of heavymetals (e.g., Mo, W, Sn, V, Zr, etc.) with phosphoric acids (e.g.,phosphomolybdic acid), and mineral acids, for example, H₂ SO₄ andphosphoric acid, are useful. The amount of catalyst used is generallysmall, ranging from about 0.01 mole % to about 10 mole %, more oftenfrom about 0.1 mole % to about 2 mole %, based on moles of olefinicreactant.

(A) The Olefinic Compound

The olefinic compound employed as a reactant in the process of thisinvention contains at least one group of the formula ##STR3## and hasthe general formula

    (R.sup.1)(R.sup.2)C═C(R.sup.6)(CH(R.sup.7)(R.sup.8))   (III)

wherein each of R¹ and R² is, independently, hydrogen or a hydrocarbonbased group. Each of R⁶, R⁷ and R⁸ is, independently, hydrogen or ahydrocarbon based group; preferably at least one is a hydrocarbon basedgroup containing at least 7 carbon atoms. These olefinic compounds arediverse in nature.

Virtually any compound containing an olefinic bond may be used providedit meets the general requirements set forth hereinabove for (III) anddoes not contain any functional groups (e.g., primary or secondaryamines) that would interfere with the carboxylic reactant (B). Usefulolefinic compounds may be terminal olefins, i.e., olefins having a H₂C═C group, or internal olefins. Useful olefinic compounds may have morethan one olefinic bond, i.e., they may be dienes, trienes, etc. Mostoften they are mono-olefinic. Examples include linear α-olefins, cis- ortrans- disubstituted olefins, trisubstituted olefins andtetrasubstituted olefins.

When (A) is a monoolefinic, one mole of (A) contains one equivalent ofC═C; when (A) is diolefinic, one mole of (A) contains 2 equivalents ofC═C bonds; when (A) is triolefinic, one mole of (A) contains 3equivalents of C═C bonds, and so forth.

Aromatic double bonds are not considered to be olefinic double bondswithin the context of this invention.

As used herein, the expression "polyolefin" defines a polymer derivedfrom olefins. The expression "polyolefinic" refers to a compoundcontaining more than one C═C bond.

Among useful compounds are those that are purely hydrocarbon, i.e.,those substantially free of non-hydrocarbon groups, or they may containone or more non-hydrocarbon groups or atoms as discussed in greaterdetail herein.

In one embodiment, the olefinic compounds are substantially hydrocarbon,that is, each R group in (III) is H or contains essentially carbon andhydrogen. In one aspect within this embodiment, each of R¹, R², R⁷ andR8 is hydrogen and R⁶ is a hydrocarbyl group containing from 7 to about5,000 carbon atoms, more often from about 30 up to about 200 carbonatoms, preferably from about 50 up to about 100 carbon atoms. In anotheraspect of this embodiment, each of R¹ and R² is hydrogen, R⁶ is H or alower alkyl group, usually methyl, and the group (CH(R⁷)(R⁸)) is ahydrocarbyl group containing from 7 to about 5,000 carbon atoms, moretypically from about 30 up to about 200 carbon atom, preferably from 50up to about 100 carbon atoms.

As used here, and throughout the specification and claims, theexpression "lower" with "alkyl", "alkenyl", etc. means groups having 7or fewer carbon atoms, for example, methyl, ethyl and all isomers ofpropyl, butyl, pentyl, hexyl and heptyl, ethylene, butylene, etc.

In another embodiment, one or more of the R groups present in (III) isan organic radical which is not purely hydrocarbon. Such groups maycontain or may be groups such as carboxylic acid, ester, amide, salt,including ammonium, amine and metal salts, cyano, hydroxy, thiol,tertiary amino, nitro, alkali metal mercapto and the like. Illustrativeof olefinic compounds (III) containing such groups are methyl oleate,oleic acid, 2-dodecenedioic acid, octene diol, linoleic acid and estersthereof, and the like.

Preferably, the hydrocarbyl groups are aliphatic groups. In onepreferred embodiment, when an R group is an aliphatic group containing atotal of from about 30 to about 200 carbon atoms, the olefinic compoundis derived from homopolymerized and interpolymerized C₂₋₁₈ mono- anddi-olefins, preferably 1-olefins. In a preferred embodiment, the olefinscontain from 2 to about 5 carbon atoms, preferably 3 or 4 carbon atoms.Examples of such olefins are ethylene, propylene, butene-1, isobutylene,butadiene, isoprene, 1-hexene, 1-octene, etc. R groups can, however, bederived from other sources, such as monomeric high molecular weightalkenes (e.g. 1-tetracontene), aliphatic petroleum fractions,particularly paraffin waxes and cracked analogs thereof, white oils,synthetic alkenes such as those produced by the Ziegler-Natta process(e.g., poly-(ethylene) greases) and other sources known to those skilledin the art. Any unsaturation in the R groups may be reduced byhydrogenation according to procedures known in the art, provided atleast one olefinic group remains as described for (III).

In one preferred embodiment, at least one R is derived from polybutene,that is, polymers of C₄ olefins, including 1-butene, 2-butene andisobutylene. Those derived from isobutylene, i.e., polyisobutylenes, areespecially preferred. In another preferred embodiment, R is derived frompolypropylene. In another preferred embodiment, R is derived fromethylene-alpha olefin polymers, including ethylene-propylene-dienepolymers. Representative of such polymers are the ethylene-propylenecopolymers and ethylene-propylene-diene terpolymers marketed under theTRILENE® tradename by the Uniroyal Company. Molecular weights of suchpolymers may vary over a wide range, but especially preferred are thosehaving number average molecular weights (M_(n)) ranging from about 300to about 20,000, preferably 700 to about 10,000, often from 900 to2,500. In one preferred embodiment, the olefin is anethylene-propylene-diene terpolymer having M_(n) ranging from about 900to about 8,000, often up to about 2,000. Such materials are includedamong the TRILENE® polymers marketed by the Uniroyal Company,Middlebury, Conn. USA and ORTHOLEUM® 2052 marketed by the DuPontCompany.

Ethylene-alpha olefin copolymers and ethylene-lower olefin-dieneterpolymers are described in numerous patent documents, includingEuropean patent publication EP 279,863, Japanese patent publication87-129,303 and the following United States patents:

U.S. Pat. No. 3,598,738

U.S. Pat. No. 4,026,809

U.S. Pat. No. 4,032,700

U.S. Pat. No. 4,137,185

U.S. Pat. No. 4,156,061

U.S. Pat. No. 4,320,019

U.S. Pat. No. 4,357,250

U.S. Pat. No. 4,668,078

U.S. Pat. No. 4,668,834

U.S. Pat. No. 4,937,299

U.S. Pat. No. 5,324,800 each of which is incorporated herein byreference for relevant disclosures of these ethylene based polymers

A preferred source of hydrocarbyl groups R are polybutenes obtained bypolymerization of a C₄ refinery stream having a butene content of 35 to75 weight percent and isobutylene content of 15 to 60 weight percent inthe presence of a Lewis acid catalyst such as aluminum trichloride orboron trifluoride. These polybutenes contain predominantly (greater than80% of total repeating units) isobutylene repeating units of theconfiguration ##STR4## These polybutenes are typically monoolefinic,that is they contain but one olefinic bond per molecule.

The olefinic compound may be a polyolefin comprising a mixture ofisomers wherein from about 50 percent to about 65 percent aretri-substituted olefins wherein one substituent contains from 2 to about5000 carbon atoms, often from about 30 to about 200 carbon atoms, moreoften from about 50 to about 100 carbon atoms, usually aliphatic carbonatoms, and the other two substituents are lower alkyl.

When the olefin is a tri-substituted olefin, it frequently comprises amixture of cis- and trans- 1-lower alkyl, 1-(aliphatic hydrocarbylcontaining from 30 to about 100 carbon atoms), 2-lower alkyl ethene and1,1-di-lower alkyl, 2-(aliphatic hydrocarbyl containing from 30 to about100 carbon atoms) ethene.

In one embodiment, the monoolefinic groups are predominantly vinylidenegroups, i.e., groups of the formula ##STR5## especially those of theformula ##STR6## although the polybutenes may also comprise otherolefinic configurations.

In one embodiment the polybutene is substantially monoolefinic,comprising at least about 30 mole %, preferably at least about 50 mole %vinylidene groups, more often at least about 70 mole % vinylidenegroups. Such materials and methods for preparing them are described inU.S. Pat. Nos. 5,071,919; 5,137,978; 5,137,980; 5,286,823 and 5,408,018,and in published European patent application EP 646103-A1, each of whichis expressly incorporated herein by reference. They are commerciallyavailable, for example under the tradenames ULTRAVIS® (BP Chemicals) andGlissopal (BASF).

Illustrative is a polyolefin comprising a mixture of isomers, at leastabout 50% by weight of the mixture comprising isomers of the formula

    H.sub.2 C═C(R.sup.6)(CH(R.sup.7)(R.sup.8))

wherein R⁶ is H or lower alkyl, preferably methyl.

As is apparent from the foregoing, olefins of a wide variety of type andmolecular weight are useful for preparing the compositions of thisinvention. Useful olefins are usually substantially hydrocarbon and havenumber average molecular weight ranging from about 100 to about 70,000,more often from about 200 to about 7,000, even more often from about1,300 to about 5,000, frequently from about 400 to about 3,000. Lowerolefins such as those containing from about 7 to about 30 carbon atoms,for example, octenes, octadecenes, mixed olefin, such as C₈₋₂₈ linearolefins, are useful.

Specific characterization of olefin reactants (A) used in the processesof this invention can be accomplished by using techniques known to thoseskilled in the art. These techniques include general qualitativeanalysis by infrared and determinations of average molecular weight,e.g., M_(n), number average molecular weight, and M_(w), weight averagemolecular weight, etc. employing vapor phase osmometry (VPO) and gelpermeation chromatography (GPC). Structural details can be elucidatedemploying proton and carbon 13 (C¹³) nuclear magnetic resonance (NMR)techniques. NMR is useful for determining substitution characteristicsabout olefinic bonds, and provides some details regarding the nature ofthe substituents. More specific details regarding substituents about theolefinic bonds can be obtained by cleaving the substituents from theolefin by, for example, ozonolysis, then analyzing the cleaved products,also by NMR, GPC, VPO, and by infra-red analysis and other techniquesknown to the skilled person.

(B) The Carboxylic Reactant

The carboxylic reactant is at least one member selected from the groupconsisting of compounds of the formula

    R.sup.3 C(O)(R.sup.4).sub.n C(O)OR.sup.5                   (IV)

and compounds of the formula ##STR7## wherein each of R³ , R⁵ and eachR⁹ is independently H or a hydrocarbyl group.

R³ is usually H or an aliphatic group, that is, alkyl or alkenyl,preferably alkyl, more preferably lower alkyl. Especially preferred iswhere R³ is H or methyl, most preferably, H.

R⁴ is a divalent hydrocarbylene group. This group may be aliphatic oraromatic, but is usually aliphatic. Often, R⁴ is an alkylene groupcontaining from 1 to about 3 carbon atoms. The `n` is 0 or 1; that is,in one embodiment R⁴ is present and in another embodiment, R⁴ is absent.More often, R⁴ is absent.

When R⁵ is hydrocarbyl, it is usually an aliphatic group, often a groupcontaining from 1 to about 30 carbon atoms, often from 8 to about 18carbon atoms. In another embodiment, R⁵ is lower alkyl, wherein "loweralkyl" is defined hereinabove, especially from 1 to 4 carbon atoms. Mostoften, R⁵ is H or lower alkyl.

R⁹ is usually H or alkyl, preferably H or lower alkyl.

Examples of carboxylic reactants (B) are glyoxylic acid, and otheromega- oxoalkanoic acids, keto alkanoic acids such as pyruvic acid,levulinic acid, ketovaleric acids, ketobutyric acids, the hemiacetals,for example glyoxylic acid methyl ester methyl hemiacetal, andhemiketals thereof, and the corresponding acetals and ketals, andnumerous others. The skilled worker, having the disclosure before him,will readily recognize the appropriate compound of formula (IV) and (V)to employ as a reactant to generate a given compound.

Reactant (B) may be a compound of the formula ##STR8## wherein each ofR³ and R⁵ is independently H or alkyl. Such compounds arise whenreactant (B) is hydrated. Glyoxylic acid monohydrate is a representativeexample.

(C) The Aldehyde or Ketone

The aldehyde or ketone reactant employed in the process of thisinvention is a carbonyl compound other than a carboxy-substitutedcarbonyl compound. Accordingly, it is to be understood that it is notcontemplated herein that reactant (C) includes any of the speciesdefined hereinabove as reactant (B). Suitable compounds include thosehaving the general formula RC(O)R', wherein R and R' are each,independently, H or a hydrocarbyl group as defined hereinabove. As notedin the description, hydrocarbyl groups may contain other groups orheteroatoms which do not interfere with the process and products of thisinvention. Preferably, reactant (C) contains from 1 to about 12 carbonatoms. Suitable aldehydes include formaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, isobutyraldehyde, pentanal, hexanal,heptaldehyde, octanal, benzaldehyde, and higher aldehydes. Otheraldehydes, such as dialdehydes, especially glyoxal, are useful, althoughmonoaldehydes are generally preferred.

The most preferred aldehyde is formaldehyde, which can be supplied asthe aqueous solution often referred to as formalin, but is more oftenused in the polymeric form as paraformaldehyde, which is a reactiveequivalent of, or a source of, formaldehyde. Other reactive equivalentsinclude hydrates or cyclic trimers.

Suitable ketones include acetone, butanone, methyl ethyl ketone, andother ketones. Preferably, one of the hydrocarbyl groups is methyl.

Mixtures of two or more aldehydes and/or ketones are also useful.

The process of this invention is conducted at temperatures ranging fromambient up to the lowest decomposition temperature of any of thereactants, usually from about 60° C. to about 220° C., more often fromabout 120° C. to about 180° C., preferably up to about 160° C. When thereaction is conducted in the presence of organic sulfonic acid ormineral acid catalyst, the reaction is usually conducted at temperaturesup to about 160° C. The process employs from about 0.6 moles of reactant(B) per mole of olefinic compound (A), up to 1.5 moles (B) perequivalent of (A), more often from about 0.8 moles (B) per mole of (A)to about 1.2 moles (B) per equivalent of (A), even more often from about0.95 moles (B) per mole of (A) to about 1.05 moles (B) per equivalent of(A). Reactant (C) is used in amounts ranging from about 0.5 to about 2moles per mole of (B), preferably, from about 0.8 to about 1.5 moles permole of (B), and most often from about 0.9 to about 1.1 moles per moleof (B). As noted herein, many reactants contain water which is removed.Removal of water at moderate temperatures is attainable employingreduced pressure, a solvent that aids in azeotropic distillation ofwater, or by purging with an inert gas such as N₂.

The progress of the reaction can be followed by observing the infra-redspectrum. The absorption for --COOH carbonyl of the products appears atabout 1710 cm⁻¹. The total acid number as measured using essentially theprocedure in ASTM D-664 (Potentiometric Method) or ASTM D-974 (ColorIndicator Method) is useful together with the infrared, keeping in mindthat non-acidic products (e.g., polyester products), those derived fromnon-acidic reactants and condensation products such as lactones will notdisplay significant acid numbers.

These procedures appear in the Annual Book of ASTM Standards, Volume05.01, ASTM, 1916 Race Street, Philadelphia, Pa. USA.

As noted hereinabove, products obtained by the process of this inventionare provided. While it appears that the product obtained by the processof this invention is a fairly complex mixture, the mixture is believedto comprise at least one composition comprising a compound of theformula ##STR9## wherein each n═0 or 1; each y═0 or 1; wherein each X isindependently a divalent hydrocarbon based group selected from the groupconsisting of ##STR10## when y═0, and ##STR11## when y═1 wherein each ofR¹, R¹¹, R², R²², R³ and R³³ is independently H or a hydrocarbon basedgroup, preferably H or lower alkyl or alkenyl; each of R⁴ and R⁴⁴ is adivalent hydrocarbylene group, preferably alkylene, more preferablycontaining 1 to about 3 carbon atoms; each A is a group of the formula##STR12## each R⁵ is independently H or a hydrocarbon based group,preferably H or lower alkyl;

each of R⁶, R⁷, and R⁸ is independently H or a hydrocarbon based group,preferably at least one being a hydrocarbon based group containing atleast 7 carbon atoms, preferably from 7 to about 5000 carbon atoms; andeach of R⁹ and R¹⁰ is independently H or a hydrocarbon based group,preferably H.

In one preferred embodiment, each of R¹, R¹¹, R², R²², R³ and R³³ is Hand n═0. Especially preferred is where each of R¹, R¹¹, R², R²² isindependently H or lower alkyl.

In one embodiment, at least one of R⁶ is an aliphatic group containingfrom about 10 to about 300 carbon atoms, especially those derived from apolymer selected from the group consisting of homopolymerized antinterpolymerized C₂₋₁₈ olefins, especially 1-olefins. The 1-olefins arepreferably ethylene, propylene, butenes, isobutylene and mixturesthereof.

In still another embodiment, R⁶ is an aliphatic group containing from 8to about 24 carbon atoms; in another embodiment, from 12 to about 50carbon atoms.

In one embodiment, X is the group ##STR13## wherein at least one of R⁷and R⁸ is an aliphatic group containing 10-300 carbon atoms, more oftenfrom about 30 to about 100 carbon atoms.

In yet another embodiment, at least one of R⁷ and R⁸ is an aliphaticgroup containing from 8 to about 24 carbon atoms; in another embodiment,from 12 to about 50 carbon atoms.

The following examples are intended to illustrate several compositionsof this invention as well as means for preparing same. Unless indicatedotherwise all parts are parts by weight, filtrations are conductedemploying a diatomaceous earth filter aid, and analytical values are byactual analysis. The abbreviations GPC and VPO refer to gel permeationchromatography and vapor phase osmometry, respectively, both proceduresbeing used to determine molecular weight. The abbreviation TLC-FIDrefers to thin layer chromatography using a flame ionization detector.Saponification numbers are determined using ASTM Procedure D-94. It isto be understood that these examples are not intended to limit the scopeof the invention.

EXAMPLE 1

A reactor is charged with 250 parts of polyisobutylene (GLISSOPAL®ES3250, BASF) having M_(n) about 1000 and containing about 87 molepercent terminal vinylidene groups, 52 parts 50% aqueous glyoxylic acid,15 parts paraformaldehyde and 1 part 70% aqueous methanesulfonic acid.These are heated with mixing, under N₂, to 160° C. and are held attemperature for a total of 4.5 hours. The materials are stripped to 135°C. and 25 millimeters Hg pressure (mm Hg) and filtered. The filtrate hassaponification no ═32.4, and contains (GPC) 96.3% material having M_(n)═1432 and M_(w) ═2157.

EXAMPLE 2

A reactor is charged with 250 parts of the polyisobutylene of Example 1,37 parts of 50% aqueous glyoxylic acid, 7.5 parts paraformaldehyde and 1part 70% aqueous methanesulfonic acid. The materials are heated withmixing under N₂, to 160° C. and are held at temperature for 5 hours,collecting 26 parts water. The materials are stripped to 125° C. and 25mm Hg and filtered. The filtrate has saponification no ═40.3, contains13.9% unreacted polyisobutylene and has (GPC) M_(n) ═1539 and M_(w)═2693.

EXAMPLE 3

Employing the same reactants as in Example 2, 1200 parts ofpolyisobutylene, 177.6 parts 50% aqueous glyoxylic acid, 4.8 parts 70%aqueous methanesulfonic acid and 36 parts paraformaldehyde are reacted,under N₂, at 160° C. for 5.5 hours, collecting 114 parts water. Thematerials are cooled to 100° C. and stripped to 140° C. and 20 mm Hg andfiltered. The filtrate has saponification no ═44 and has (VPO) M_(n)═1852.

EXAMPLE 4

Employing the same reactants as in Example 2, 3000 parts ofpolyisobutylene, 444 parts, 444 parts 50% aqueous glyoxylic acid, 12parts 70% aqueous methanesulfonic acid and 99 parts paraformaldehyde arereacted, under N₂ at 160° C. for 5 hours, collecting 344 parts waterthen for an additional 3 hours. The materials are cooled then strippedto 160° C. and 30 mm Hg and filtered. The filtrate has saponification no═44, has (GPC) M_(n) ═1450 and contains 17% unreacted polyisobutylene.

EXAMPLE 5

Employing the same reactants as in Example 2, 3000 parts ofpolyisobutylene, 488 parts 50% aqueous glyoxylic acid, 12 parts 70%aqueous methanesulfonic acid and 99 parts paraformaldehyde are reacted,under N₂, at 120° C. for hours, collecting water then at 160° C. for 5hours, collecting water. The materials are cooled to 140° C. andfiltered. The filtrate has saponification no ═50, has (GPC) M_(n) ═1475,M_(w) ═2422 and contains 15 % unreacted polyisobutylene.

EXAMPLE 6

A reactor is charged with 832 parts of polyisobutylene (GLISSOPALES3252) having M_(n) about 2400 and containing about 70 mole percentterminal vinylidene groups, 61.6 parts 50% aqueous glyoxylic acid, 13.7parts paraformaldehyde, 3 parts 70% aqueous methanesulfonic acid, and571.2 parts mineral oil. The materials are heated to 120° C. over 1hour, collecting water, then to 160° C. over 1 hour, reacted at 160° C.for 8 hours, while collecting water. The materials are stripped to 160°C. and 25 mm Hg and filtered at 140° C. The filtrate has saponificationno ═13.4. (GPC) M_(n) ═4324, M_(w) ═9779 (65 %) and M_(n) ═340, M_(w)═412. (35%).

EXAMPLE 7

A reactor is charged with 4000 parts polyisobutylene (ULTRAVIS® 10, BPChemicals) having M_(n) about 1000 and containing about 80 mole %terminal vinylidene groups, 592 parts 50% aqueous glyoxylic acid, 132parts paraformaldehyde and 16 parts 70% aqueous methanesulfonic acid.The materials are heated to 120° C. over 0.75 hour then to 160° C. over2.5 hours, collecting water, then reacted at 160° C for a total of 6hours; total water collected, 475 parts. The materials are stripped to160° C. and 40 mm Hg and filtered. The filtrate contains 19.9% unreactedpolyisobutylene, has saponification no. ═42 and (GPC) M_(n) ═1419, M_(w)═3272.

EXAMPLE 8

The procedure of Example 2 is repeated replacing the glyoxylic acid withan equivalent amount of pyruvic acid.

EXAMPLE 9

The procedure of Example 4 is repeated replacing glyoxylic acid with anequivalent amount of levulinic acid.

EXAMPLE 10

The procedure of Example 1 is repeated replacing glyoxylic acid with anequivalent amount of glyoxylic acid methyl ester methyl hemiacetal.

EXAMPLE 11

The procedure of Example 4 is repeated replacing glyoxylic acid with anequivalent amount of glyoxylic acid methyl ester methyl hemiacetal.

EXAMPLE 12

A reactor is charged with 1000 parts of the polyisobutylene used inExample 1, 148 parts of 50% aqueous glyoxylic acid, 29 parts glyoxal and2 parts 70% aqueous methane sulfonic acid. Under N₂, the materials areheated to 130° C., held at 130° C. for 2 hours, heated to 160° C., andheld at 160° C. for 4 hours, while collecting a total of 108 partsaqueous distillate. The materials are mixed with 730.7 parts mineral oiland filtered at 140° C. obtaining a filtrate having total acid no ═11.8and saponification no ═26.5.

EXAMPLE 13

A reactor is charged with 800 parts of the polyisobutylene used inExample 1, 118.4 parts of 50% aqueous glyoxylic acid, 18.6 parts glyoxaland 1.6 parts 70% aqueous methane sulfonic acid. Under N₂, the materialsare heated to 140° C., held at 140°-148° C. for 6 hours, then at 145° C.for 7 hours, while collecting aqueous distillate. The materials aremixed with 567 parts mineral oil and filtered at 145° C. obtaining afiltrate having total acid no ═0, saponification no ═23.2 and (GPC)59.94% M_(n) ═1743, M_(w) ═2184; 40.1% M_(n) ═358.

EXAMPLE 14

A reactor is charged with 1000 parts of the polyisobutylene used inExample 1, 37 parts 50% aqueous glyoxylic acid, 35.6 parts nonylaldehyde and 1 part 70% aqueous methane sulfonic acid. The materials areheated, under N₂, to 160° C. and are held at 160° C. for 5 hours whilecollecting 23.9 parts aqueous distillate. The materials are stripped to125° C. at 56 mm Hg, then filtered at 20° C. The filtrate has total acidno. ═14.8, saponification no. ═36.4 and, by GPC, 100% M_(n) 1191, M_(w)1881, and contains 25% unreated polyisobutylene (TLC-FID).

EXAMPLE 15

The procedure of Example 1 is repeated replacing the paraformaldehydewith 29 parts acetone.

EXAMPLE 16

The procedure of Example 6 is repeated replacing paraformaldehyde with58 parts 2-octanone.

EXAMPLE 17

The procedure of Example 7 is repeated replacing paraformaldehyde with729 parts benzophenone.

While the invention has been explained in relation to its preferredembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein is intended to cover such modifications that fallwithin the scope of the appended claims.

What is claimed is:
 1. A composition comprising a compound of theformula ##STR14## wherein each n=0 or 1; each y=0 or 1; wherein each Xis independently a divalent hydrocarbon based group selected from thegroup consisting of ##STR15## when y=0, and ##STR16## when y=1 whereineach of R¹, R¹¹, R², and R²² is independently H or a hydrocarbon basedgroup;each of R³ and R³³ is independently H or a hydrocarbon basedgroup: each of R⁴ and R⁴⁴ is a divalent hydrocarbylene group; each A isa group of the formula ##STR17## each R⁵ is independently H or ahydrocarbon based group; each of R⁶, R⁷, and R⁸ is independently H or ahydrocarbon based group; and each of R⁹ and R¹⁰ is independently H or ahydrocarb on based group.
 2. The composition of claim 1 wherein at leastone of R⁶, R⁷, and R⁸ is a hydrocarbon based group containing at least 7carbon atoms.
 3. The composition of claim 1 wherein each of R¹, R¹¹, R²,R²², R³, and R³³ is independently H and n=0.
 4. The composition of claim1 wherein each of R⁴ and R⁴⁴ is an alkylene group containing from 1 toabout 3 carbon atoms.
 5. The composition of claim 1 wherein each of R¹,R¹¹, R², R²², R³, and R³³ is independently H and n=zero.
 6. Thecomposition of claim 1 wherein each X has the formula. ##STR18##
 7. Thecomposition of claim 1 wherein each X has the formula. ##STR19##
 8. Thecomposition of claim 7 wherein at least one of R⁶, R⁷, and R⁸ is ahydrocarbon based group containing from about 7 to about 5000 carbonatoms.
 9. The composition of claim 7 wherein at least one R⁶ is analiphatic group containing from about 10 to about 300 carbon atoms. 10.The composition of claim 9 wherein each R⁶ contains from 30 to about 100carbon atoms and is derived from a polymer selected from the groupconsisting of homopolymerized and interpolymerized C₂₋₁₈ olefins. 11.The composition of claim 6 wherein at least one of R⁷ and R⁸ is analiphatic group containing from about 10 to about 300 carbon atoms. 12.The composition of claim 11 wherein at least one of R⁷ and R⁸ containsfrom about 30 to about 100 carbon atoms and is derived from a polymerselected from the group consisting of homopolymerized andinterpolymerized C₂₋₁₈ olefins.
 13. The composition of claim 10 whereinthe olefins are 1-olefins.
 14. The composition of claim 13 wherein the1-olefins are ethylene, propylene, butenes, isobutylene and mixturesthereof.
 15. The composition of claim 1 wherein at least one of R⁷ andR⁸ is an aliphatic group containing from 8 to about 24 carbon atoms. 16.The composition of claim 1 wherein at least one of R⁷ and R⁸ containsfrom 12 to about 50 carbon atoms.
 17. The composition of claim 7 whereinR⁶ is an aliphatic group containing from 8 to about 24 carbon atoms. 18.The composition of claim 7 wherein R⁶ contains from 12 to about 50carbon atoms.
 19. The composition of claim 1 wherein each of R¹, R¹¹, R²and R²² is independently H or lower alkyl.
 20. The composition of claim1 wherein R⁵ is H or a lower alkyl group.
 21. The composition of claim 1wherein each of R⁹ and R¹⁰ is H.